沼气中含有硫化氢，分子式为H2S，硫化氢为易燃危化品，与空气混合能形成爆炸性混合物，遇明火、高热能引起燃烧爆炸，加上硫化氢遇水后会对钢材产生较强的腐蚀特性，因此沼气提纯精制生物天然气的预处理工序的核心即是脱除硫化氢。

Biogas contains hydrogen sulfide, with a molecular formula of H2S. Hydrogen sulfide is a flammable and hazardous chemical that can form explosive mixtures when mixed with air. When exposed to open flames and high heat, it can cause combustion and explosion. In addition, hydrogen sulfide has strong corrosion characteristics on steel when it comes into contact with water. Therefore, the core of the pre-treatment process for purifying and refining biogas is the removal of hydrogen sulfide.

不同的有机废弃物在厌氧状态下产生的沼气中的硫化氢浓度有高有低，差异比较大。造纸工业、发酵工业等由于在生产过程中有含硫的介质加入，生产废水产生的沼气含硫化氢的浓度便比较高。如造纸行业的沼气可高达10000-35000ppm，淀粉工业沼气一般在10000ppm左右，生活垃圾填埋沼气则由于产生过程中相对较少有硫介质参与，因此硫化氢含量较低，一般在1000ppm以内。

The concentration of hydrogen sulfide in biogas produced by different organic wastes under anaerobic conditions varies greatly, with varying levels. Due to the addition of sulfur-containing media in the production process, the concentration of hydrogen sulfide in the biogas produced from production wastewater is relatively high in industries such as papermaking and fermentation. For example, the biogas in the papermaking industry can reach up to 10000-35000ppm, while the biogas in the starch industry is generally around 10000ppm. For landfill biogas in household waste, the hydrogen sulfide content is relatively low, usually within 1000ppm, due to the relatively low involvement of sulfur media in the production process.

在我国，沼气的生产加工技术和商业化运行系统也已经逐渐成熟，通过自主创新、引进并消化吸收了国外成熟的高含固量的有机废弃物厌氧消化技术，其中以谷物秸秆、畜禽粪便、城市有机垃圾为处理对象的大型沼气工程也取得了突破性进展，因此，相应的沼气净化工艺技术也得到发展，形成了一系列相对比较成熟的技术。

In China, the production and processing technology and commercial operation system of biogas have gradually matured. Through independent innovation, introduction, and digestion, advanced anaerobic digestion technology for high solid organic waste from abroad has been absorbed. Among them, large-scale biogas projects that treat grain straw, animal manure, and urban organic waste have also made breakthrough progress. Therefore, corresponding biogas purification process technologies have also been developed, A series of relatively mature technologies have been formed.

行业内常用的沼气脱硫方法有：干法脱硫、湿法脱硫、络合铁脱硫、生物法脱硫等几种脱硫方法。

The commonly used biogas desulfurization methods in the industry include dry desulfurization, wet desulfurization, complex iron desulfurization, and biological desulfurization.

脱硫原理

Desulfurization principle

干法脱硫

Dry desulfurization

唐山绿干法脱硫是一种简易、、相对低成本的脱硫方式，一般适合用于沼气量小，硫化氢浓度低的沼气脱硫。干法脱除沼气气体中硫化氢（H2S）的设备基本原理是以O2使H2S 氧化成硫或硫氧化物的一种方法，也可称为干式氧化法。干法设备的构成是，在一个容器内放入填料，填料层有活性炭、氧化铁等。气体以低流速从一端经过容器内填料层，硫化氢（H2S）氧化成硫或硫氧化物后，余留在填料层中，净化后气体从容器另一端排出。

Tangshan Green Dry Desulfurization is a simple, efficient, and relatively low-cost desulfurization method, generally suitable for biogas desulfurization with small biogas volume and low hydrogen sulfide concentration. The basic principle of the equipment for dry removal of hydrogen sulfide (H2S) from biogas gas is a method of using O2 to oxidize H2S into sulfur or sulfur oxides, also known as dry oxidation method. The composition of dry process equipment is to place fillers in a container, and the filler layer includes activated carbon, iron oxide, etc. The gas passes through the packing layer inside the container at a low flow rate, and hydrogen sulfide (H2S) is oxidized to sulfur or sulfur oxides, remaining in the packing layer. After purification, the gas is discharged from the other end of the container.

干式脱硫主要包括主体钢结构、脱硫剂填料、观察窗、压力表、温度表等组件。脱硫塔通常设计为一用一备，交替使用，即一个脱硫，一个再生。 含有硫化氢(H2S)的沼气进入脱硫塔底部，在穿过脱硫填料层到达顶端的过程中，H2S与脱硫剂发生以下的化学反应：

Dry desulfurization mainly includes components such as main steel structure, desulfurizer filler, observation window, pressure gauge, temperature gauge, etc. Desulfurization towers are usually designed as one for use and one for backup, alternating between one for desulfurization and one for regeneration. Biogas containing hydrogen sulfide (H2S) enters the bottom of the desulfurization tower and undergoes the following chemical reactions with the desulfurizer during the process of passing through the desulfurization packing layer and reaching the top:

步: Fe2O3 · H2O + 3 H2S = Fe2S3 + 4 H2O （脱硫）

Step 1: Fe2O3 · H2O+3 H2S=Fe2S3+4 H2O (desulfurization)

第二步: Fe2S3 + 3/2 O2 + 3 H2O = Fe2O3 · H2O + 2 H2O + 3 S（再生）

Step 2: Fe2S3+3/2 O2+3 H2O=Fe2O3 · H2O+2 H2O+3 S (regeneration)

含有硫化氢的沼气与底部入口处荷载相对高的脱硫剂反应，反应器上部是负载低的脱硫剂层，通过设计良好的沼气空速和线速，干式脱硫能到达良好的精脱硫效果。

Biogas containing hydrogen sulfide first reacts with a desulfurizer with a relatively high load at the bottom inlet. The upper part of the reactor is a desulfurizer layer with a low load. By designing good biogas airspeed and line speed, dry desulfurization can achieve good precision desulfurization effect.

在沼气进入干式脱硫塔之前，应设置有冷凝水罐或沼气颗粒过滤器。该装置可以沼气中夹杂的颗粒杂质，并使得沼气在进入脱硫前含有一定湿度。

Before biogas enters the dry desulfurization tower, a condensate tank or biogas particle filter should be installed. This device can eliminate particle impurities in biogas and make biogas contain a certain humidity before entering desulfurization.

当观察到脱硫剂变色，或系统压力损失过大时，应交替使用另一个脱硫塔。当前的脱硫塔在沼气放空后，进行自然通风，对脱硫剂进行再生。当再生效果不佳时，应从塔体底部将废弃的脱硫剂排除，在底部排放废弃填料的同时，相同体积的新鲜脱硫填料加入反应器中。

When discoloration of the desulfurizer or excessive pressure loss in the system is observed, another desulfurization tower should be used alternately. The current desulfurization tower undergoes natural ventilation after releasing biogas to regenerate the desulfurizer. When the regeneration effect is poor, the waste desulfurizer should be discharged from the bottom of the tower. At the same time as the waste packing is discharged at the bottom, fresh desulfurized packing of the same volume should be added to the reactor.

切记更换脱硫剂时不可时间过短，否则很容易引起放热导致硫磺自燃。

Remember not to replace the desulfurizer for too short a time, otherwise it is easy to cause heat release and sulfur self ignition.

湿法脱硫

Wet desulfurization

湿法脱硫可以归纳分为物理吸收法、化学吸收法和氧化法三种。物理和化学方法存在硫化氢再处理问题，氧化法是以碱性溶液为吸收剂，并加入载氧体为催化剂，吸收H2S，并将其氧化成单质硫，湿法氧化法是把脱硫剂溶解在水中，液体进入设备，与沼气混合，沼气中的硫化氢（H2S）与液体产生氧化反应，生成单质硫吸收硫化氢的液体有氢氧化钠、氢氧化钙、碳酸钠、硫酸亚铁等。成熟的氧化脱硫法，脱硫效率可达99.5%以上。

Wet desulfurization can be classified into three types: physical absorption method, chemical absorption method, and oxidation method. There is a problem of hydrogen sulfide reprocessing in physical and chemical methods. The oxidation method uses alkaline solution as an absorbent and oxygen carrier as a catalyst to absorb H2S and oxidize it into elemental sulfur. The wet oxidation method dissolves the desulfurizer in water, and the liquid enters the equipment and mixes with biogas. Hydrogen sulfide (H2S) in biogas reacts with the liquid to generate elemental sulfur. The liquids that absorb hydrogen sulfide include sodium hydroxide, calcium hydroxide, sodium carbonate, etc Ferrous sulfate, etc. The mature oxidation desulfurization method can achieve a desulfurization efficiency of over 99.5%.

在大型的脱硫工程中，一般采用先用湿法进行粗脱硫，之后再通过干法进行精脱硫。

In large-scale desulfurization projects, wet desulfurization is generally used first for coarse desulfurization, and then dry desulfurization is used for fine desulfurization.

湿法脱硫塔主体包括洗涤塔、硫化氢采样与监测系统、碱液配置槽、供水软水装置、液位控制系统、支撑件和连接件。脱硫系统通过对出气硫化氢浓度的监控以及PH值监控，实现全自动运行。

The main body of the wet flue gas desulfurization tower includes a washing tower, a hydrogen sulfide sampling and monitoring system, an alkali solution preparation tank, a water supply softening device, a liquid level control system, supporting components, and connecting components. The desulfurization system achieves fully automatic operation by monitoring the concentration of hydrogen sulfide in the outlet gas and pH value.

运行时，沼气由下上通过脱硫塔，Na2CO3溶液（或NaOH溶液）从顶部向下喷淋，使得H2S气体与碱液发生了充分的化学反应。

During operation, biogas passes through the desulfurization tower from bottom to top, and Na2CO3 solution (or NaOH solution) is sprayed downwards from the top, causing sufficient chemical reaction between H2S gas and alkaline solution.

碱液存储在脱硫塔的下方，通过计量泵自动添加，计量泵的添加控制通过对出气H2S浓度的监控自动运行。

Alkali solution is stored below the desulfurization tower and automatically added through a metering pump. The addition control of the metering pump operates automatically by monitoring the H2S concentration in the outlet gas.

当采用碳酸钠（Na2CO3）试剂脱硫时，主要发生如下反应：

When using sodium carbonate (Na2CO3) reagent for desulfurization, the following reactions mainly occur:

H2S + Na2CO3 = NaHS + NaHCO3 ( 1 )

H2S+Na2CO3=NaHS+NaHCO3 (1)

CO2 + Na2CO3 + H2O = 2 NaHCO3 ( 2 )

CO2+Na2CO3+H2O=2 NaHCO3 (2)

由于沼气中含有的大量CO2成分，同样会消耗碱液。 系统应能对反应条件（包括反应温度、PH值）等进行控制，设置反应条件，尽可能地减少碱液的消耗量。

Due to the large amount of CO2 contained in biogas, it also consumes alkaline solution. The system should be able to control the reaction conditions (including reaction temperature, pH value), set the optimal reaction conditions, and minimize the consumption of alkaline solution as much as possible.

络合铁脱硫

Complex iron desulfurization

络合铁工艺是一种绿色的，基于Fe基催化剂的湿法气体净化技术，它集脱硫与硫磺回收于一体，在液相中直接将H2S转化为单质S。

The complex iron process is a green, Fe based catalyst based wet gas purification technology that integrates desulfurization and sulfur recovery. It directly converts H2S into elemental S in the liquid phase.

硫化氢脱出率高（ 一步反应的脱出率99.99+% ）

High hydrogen sulfide extraction rate (99.99+% of one-step reaction)

工艺简单、，系统不使用任何有毒的化学物质，也不会产生任何有害的废弃物，控制简单，系统系数高

The process is simple and safe, and the system does not use any toxic chemicals or produce any harmful waste. The control is simple, and the system has a high safety factor

适合于产量在200公斤-20吨/天的小型硫化氢脱除装置

Suitable for small hydrogen sulfide removal devices with a production capacity of 200 kg -20 tons/day

适应H2S含量在0~100%

Adapt to H2S content between 0% and 100%

操作条件为常温

Operating conditions are at room temperature

唐山绿源络合铁工艺反应原理：

The reaction principle of Tangshan Green Source Complex Iron Process:

吸收反应：

Absorption reaction:

H2S(气体)+ 2Fe+++ 2H+ + S °+ 2Fe++

H2S (gas)+2Fe++2H++S °+2Fe++

再生反应：

Regenerative reaction:

1/2 O2 (气体) + H2O + 2Fe++ 2OH- + 2Fe+++

1/2 O2 (gas)+H2O+2Fe++2OH -+2Fe+++

总反应：

Total reaction:

H2S + ? O2 H2O + S°

H2S+? O2 H2O+S °

络合铁脱硫优势

Advantages of desulfurization with complex iron

（1）络合铁催化剂，工艺处理过程简单，采用一步法处理工艺即可快速将硫化氢直接氧化为硫单质；对各种不同浓度的H2S，其脱硫后的H2S含量可低于10ppm，H2S效率高。

(1) The complex iron catalyst has a simple process, and the one-step treatment process can quickly oxidize hydrogen sulfide directly to sulfur elemental; For various concentrations of H2S, the H2S content after desulfurization can be lower than 10ppm, and the removal efficiency of H2S is high.

（2）系统的抗波动能力强。对于传统的脱硫装置，原料气中硫化氢含量波动较大时，会造成出口净化气的硫化氢含量波动很大，甚超标。络合铁高硫容特性，其脱硫装置完全能自动处理以上波动情况，并不需要人为改变操作且不会影响脱硫率。

(2) The system has strong resistance to fluctuations. For traditional desulfurization devices, when the hydrogen sulfide content in the feed gas fluctuates greatly, it can cause significant fluctuations in the hydrogen sulfide content of the outlet purified gas, even exceeding the standard. The high sulfur capacity of complex iron allows its desulfurization device to automatically handle the above fluctuations without the need for manual changes in operation and without affecting the desulfurization rate.

（3）运行成本低。由于在脱硫过程中所使用的各种药剂中的络合铁催化剂可再生循环使用且无副反应发生，只需补充少量的在脱硫过程中损失的络合铁催化剂，产出一吨硫磺药剂运行成本1000-1500元。

(3) Low operating costs. Due to the renewable and recyclable use of complex iron catalysts in various reagents used in the desulfurization process without any side reactions, only a small amount of complex iron catalysts lost during the desulfurization process need to be supplemented, resulting in an operating cost of 1000-1500 yuan for producing one ton of sulfur reagents.

（4）络合铁催化剂选择性高，副盐产生量低。在络合铁脱硫中，络合铁离子氧化硫化氢为硫磺，脱硫过程副反应少，药剂使用寿命长。

(4) Complex iron catalysts have high selectivity and low bysalt production. In complex iron desulfurization, complex iron ions oxidize hydrogen sulfide to sulfur, resulting in fewer side reactions and longer service life of the reagents.

（5）脱硫工作液硫容量高。开发的络合铁脱硫剂，脱硫剂循环液的硫容量不受二氧化碳的影响，其工作硫容量高达3.3kg硫磺/m药剂，高于国外同类技术（工作硫容量较好的为0.37 kg硫磺/m药剂）。故使用络合铁脱硫剂能显著降低循环液量，降低设备尺寸，减少投资和操作成本。

(5) The desulfurization working fluid has a high sulfur capacity. The latest developed complex iron desulfurizer has a sulfur capacity that is not affected by carbon dioxide in the circulating solution of the desulfurizer. Its working sulfur capacity is as high as 3.3kg sulfur/m reagent, which is higher than similar foreign technologies (the one with better working sulfur capacity is 0.37 kg sulfur/m reagent). Therefore, the use of complex iron desulfurizers can significantly reduce the circulating liquid volume, reduce equipment size, and reduce investment and operating costs.

（6）能脱除有机硫COS、硫醇。

(6) Can remove organic sulfur COS and thiols.

（7）设备尺寸小，可有效实现橇装化。由于工作硫容量高，设备小，可有效实现橇装化，非常适合小项目的橇装化要求。

(7) The device has a small size and can effectively achieve sled installation. Due to its high working sulfur capacity and small equipment, it can effectively achieve sled mounted requirements, making it very suitable for small projects.

（8）催化剂的性高，系统所采用的催化剂对环境及人体无害，具有良好的环保效益。

(8) The safety of the catalyst is high, and the catalyst used in the system is non-toxic and harmless to the environment and human body, with good environmental benefits.

（9）系统无大量副盐产生，环保经济。

(9) The system does not produce a large amount of by-products, which is environmentally friendly and economical.

生物脱硫

Biological desulfurization

生物脱硫技术包括生物过滤法、生物吸附法和生物滴滤法，三种系统均属开放系统，其微生物种群随环境改变而变化。在生物脱硫过程中，氧化态的含硫污染物必须先经生物还原作用生成硫化物或H2S然后再经生物氧化过程生成单质硫，才能去除。在大多数生物反应器中，微生物种类以细菌为主，真菌为次，极少有酵母菌。常用的细菌是硫杆菌属的氧化亚铁硫杆菌，脱氮硫杆菌及排硫杆菌。成功的代表是氧化亚铁硫杆菌，其生长的p

Biological desulfurization technology includes biological filtration, biological adsorption, and biological drip filtration, all of which belong to open systems, and their microbial populations change with environmental changes. In the process of biological desulfurization, oxidized sulfur-containing pollutants must first undergo biological reduction to generate sulfides or H2S, and then undergo biological oxidation to generate elemental sulfur in order to be removed. In most bioreactors, the microbial species are mainly bacteria, followed by fungi, and there are very few yeast. The commonly used bacteria are Thiobacillus ferrooxidans, Thiobacillus denitrifying, and Thiobacillus excreting. The most successful representative is Thiobacillus ferrooxidans, which has the best growth rate

H值为2.0～2.2。

The H value ranges from 2.0 to 2.2.

沼气生物脱硫是20世纪90年代发展起来的新技术，在国外已得到了广泛研究，在应用方面也取得了很大进展。国外已有较成熟的沼气生物脱硫集成技术。

Biodesulfurization of biogas is a new technology developed in the 1990s, which has been widely studied abroad and has made great progress in application. There are already mature integrated technologies for biogas biological desulfurization in foreign countries.

工艺描述：

Process description:

将一定量的空气导入含有硫化氢的沼气中，混合气体通过EnvironTec生物脱硫塔去除硫化氢。在反应器内部安装有特殊的塑料填料，它们为脱硫细菌繁殖提供充分的空间。营养液的循环使填料保持潮湿状态，并且补充脱硫细菌生长繁殖所需的营养。专属菌种（如丝硫菌属或者硫杆菌属），借助营养液在填料中繁殖。在这种情况下，他们从混合沼气中吸收硫化氢，并将他们转化为单质硫，进而转化为稀硫酸，

Introduce a certain amount of air into biogas containing hydrogen sulfide, and remove the hydrogen sulfide from the mixed gas through the EnvironTec biological desulfurization tower. Special plastic fillers are installed inside the reactor, providing ample space for the proliferation of desulfurization bacteria. The circulation of nutrient solution keeps the filler moist and supplements the nutrients needed for the growth and reproduction of desulfurization bacteria. Exclusive bacterial species (such as Thiobacillus or Thiobacillus) can reproduce in fillers using nutrient solution. In this case, they absorb hydrogen sulfide from the mixed biogas and convert it into elemental sulfur, which in turn converts into dilute sulfuric acid,

化学反应式如下：H2S + 2O2=H2SO42

The chemical reaction formula is as follows: H2S+2O2=H2SO42

H2S + O2 =2 S + 2H2OS + H2O + 1.5 O2=H2SO4

H2S+O2=2 S+2H2OS+H2O+1.5 O2=H2SO4

生成的稀硫酸在营养液和自来水的缓冲中和作用下，一起排出系统，

The generated dilute sulfuric acid is discharged from the system together with the buffering and neutralization effect of nutrient solution and tap water,

此过程周而复始。

This process repeats itself.

1 反应塔 5 营养液供应 9 热交换器 13 营养液液位控制器

1 reaction tower 5 nutrient solution supply 9 heat exchanger 13 nutrient solution level controller

2 填料 6 稀释用水 10 气分析仪 14 空气流量计

2 fillers 6 dilution water 10 gas analyzer 14 air flow meter

3 沼气入口 7 循环液 11 pH 控制仪 15 营养液废液排出口

3 biogas inlet 7 circulating liquid 11 pH controller 15 nutrient solution waste liquid discharge outlet

4 空气供应 8营养液泵 12 温度计 16流量控制开关

4 Air supply 8 Nutrient solution pump 12 Thermometer 16 Safety flow control switch

沼气（3）进入反应器（1）底端，并从底端穿过填料层到达顶部。空气（4）通过变频控制精确添加。尾气成分分析仪（10）对余氧浓度监控并与空气风机连锁。 循环液通过循环泵（8）循环喷淋。液位开关（13）控制整体的液位平衡。为了保证细菌的活性，采用热交换器（9）和温度监测（12）对系统温度调节控制。PH仪（11）用于控制营养液的质量（酸碱度），例如当PH低于设定值时，新鲜的营养液（5）和稀释用水（6）自动加入脱硫塔中，在此同时，废液（15）自动排出，并保持液位平衡。

Biogas (3) enters the bottom of reactor (1) and passes through the packing layer from the bottom to the top. Air (4) is precisely added through frequency conversion control. The exhaust gas composition analyzer (10) monitors the residual oxygen concentration and interlocks with the air fan. The circulating liquid is sprayed through the circulating pump (8). The liquid level switch (13) controls the overall liquid level balance. To ensure optimal bacterial activity, a heat exchanger (9) and temperature monitoring (12) are used to regulate and control the system temperature. The pH meter (11) is used to control the quality (acidity) of the nutrient solution. For example, when the pH is below the set value, fresh nutrient solution (5) and dilution water (6) are automatically added to the desulfurization tower. At the same time, the waste liquid (15) is automatically discharged and the liquid level is maintained in equilibrium.

方法比较

Method comparison

干法脱硫的特点

The characteristics of dry desulfurization

结构简单，使用方便。

Simple structure and convenient use.

工作过程中无需人员值守，定期换料，一用一备，交替运行。

During the work process, there is no need for personnel to be on duty, and materials are changed regularly. One in use and one on standby operate alternately.

脱硫率新原料时较高，后期有所降低。

The desulfurization rate of new raw materials is relatively high, but it decreases in the later stage.

与湿式相比，需要定期换料。

Compared to wet type, regular material changes are required.

运行费用偏高。

The operating costs are relatively high.

湿法脱硫的特点

The characteristics of wet desulfurization

设备可长期不停的运行，连续进行脱硫。

The equipment can operate non-stop for a long time and continuously carry out desulfurization.

用PH值来保持脱硫效率，运行费用低。

Using a pH value to maintain desulfurization efficiency results in low operating costs.

工艺复杂需要专人值守。

The process is complex and requires dedicated personnel to be on duty.

设备需保养。

The equipment needs maintenance.

络合铁脱硫特点

Characteristics of desulfurization with complex iron

率： 硫化氢去除率高达99.9%

High efficiency: hydrogen sulfide removal rate up to 99.9%

高适应范围： 可处理硫化氢浓度高达100%

High adaptability range: can handle up to 100% hydrogen sulfide concentration

低成本： 与其它脱硫技术相比，运行成本

Low cost: Compared to other desulfurization technologies, the operating cost is the lowest

高性: 设有多重的保护装置

High security: equipped with multiple safety protection devices

无人值守： 系统通过在线监测系统全自动运行

Unattended: The system operates fully automatically through online monitoring system

维护简单： 少量的维护工作

Easy maintenance: minimal maintenance work

生物脱硫的特点

The characteristics of biological desulfurization

率： 硫化氢去除率高达98.5%

High efficiency: hydrogen sulfide removal rate up to 98.5%

高适应范围： 可处理硫化氢浓度高达0.8% （8000ppm）

High adaptability range: capable of handling hydrogen sulfide concentrations up to 0.8% (8000ppm)

低成本： 运行成本低

Low cost: Low operating cost

适应性: 较化学法抗波动能力差

Adaptability: Poor resistance to fluctuations compared to chemical methods

无人值守： 系统通过在线监测系统全自动运行

Unattended: The system operates fully automatically through online monitoring system

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